Particles surface

Figure V-8 illustrates that there can be a pH of zero potential interpreted as the point of zero charge at the shear plane this is called the isoelectric point (iep). Because of specific ion and Stem layer adsorption, the iep is not necessarily the point of zero surface charge (pzc) at the particle surface. An example of this occurs in a recent study of zircon (ZrSi04), where the pzc measured by titration of natural zircon is 5.9 0.1...

Energetic particles interacting can also modify the structure and/or stimulate chemical processes on a surface. Absorbed particles excite electronic and/or vibrational (phonon) states in the near-surface region. Some surface scientists investigate the fiindamental details of particle-surface interactions, while others are concerned about monitormg the changes to the surface induced by such interactions. Because of the importance of these interactions, the physics involved in both surface analysis and surface modification are discussed in this section. 

Below are brief descriptions of some of the particle-surface interactions important in surface science. The descriptions are intended to provide a basic understanding of how surfaces are probed, as most of the infonuation that we have about surfaces was obtained tluough the use of techniques that are based on such interactions. The section is divided into some general categories, and the important physics of the interactions used for analysis are emphasized. All of these teclmiques are described in greater detail in subsequent sections of the encyclopaedia. Also, note that there are many more teclmiques than just those discussed here. These particular teclmiques were chosen not to be comprehensive, but instead to illustrate the kind of infonuation that can be obtained from surfaces and interfaces. 

Initially in ceramic powder processing, particle surfaces are created tliat increase tlie surface energy of tlie system. During shape fomiing, surface/interface energy and interiiarticle forces are controlled witli surface active additives. 

Lubricants are added to lower interfacial frictional forces between individual particles and/or between particles and fonning die surfaces to improve compaction and ejection (i.e. extraction of the pressed compact from the fonning die). Individual particle surfaces can be lubricated by an adsorbed film that produces a smoother surface and/or decreases interiDarticle attraction. Fonning (die) surfaces can be lubricated by coating with a film of low-viscosity liquid such as water or oil. 

An additional method for increasing particle size deserves mention. When a precipitate s particles are electrically neutral, they tend to coagulate into larger particles. Surface adsorption of excess lattice ions, however, provides the precipitate s particles with a net positive or negative surface charge. Electrostatic repulsion between the particles prevents them from coagulating into larger particles. 

In all of these derivations concerning rigid bodies, no other walls are considered except the particle surfaces. Before we turn to the question of the intrinsic viscosity of flexible polymers, let us consider the relationship between the viscosity of a fluid and the geometry and dimensions of the container in which it is measured. 

Monomer compositional drifts may also occur due to preferential solution of the styrene in the mbber phase or solution of the acrylonitrile in the aqueous phase (72). In emulsion systems, mbber particle size may also influence graft stmcture so that the number of graft chains per unit of mbber particle surface area tends to remain constant (73). Factors affecting the distribution (eg, core-sheU vs "wart-like" morphologies) of the grafted copolymer on the mbber particle surface have been studied in emulsion systems (74). Effects due to preferential solvation of the initiator by the polybutadiene have been described (75,76). 

In addition to graft copolymer attached to the mbber particle surface, the formation of styrene—acrylonitrile copolymer occluded within the mbber particle may occur. The mechanism and extent of occluded polymer formation depends on the manufacturing process. The factors affecting occlusion formation in bulk (77) and emulsion processes (78) have been described. The use of block copolymers of styrene and butadiene in bulk systems can control particle size and give rise to unusual particle morphologies (eg, coil, rod, capsule, cellular) (77). 

For a step change in sorbate concentration at the particle surface (r = R) at time 2ero, assuming isothermal conditions and diffusion control, the expression for the uptake curve maybe derived from the appropriate solution of this differential equation ... 

To obtain an indication of the rate of solute transfer from the particle surface to the bulk of the Hquid, the concept of a thin film providing the resistance to transfer can be used (2) and the equation for mass transfer written as ... 

When initiator is first added the reaction medium remains clear while particles 10 to 20 nm in diameter are formed. As the reaction proceeds the particle size increases, giving the reaction medium a white milky appearance. When a thermal initiator, such as AIBN or benzoyl peroxide, is used the reaction is autocatalytic. This contrasts sharply with normal homogeneous polymerizations in which the rate of polymerization decreases monotonicaHy with time. Studies show that three propagation reactions occur simultaneously to account for the anomalous auto acceleration (17). These are chain growth in the continuous monomer phase chain growth of radicals that have precipitated from solution onto the particle surface and chain growth of radicals within the polymer particles (13,18). 

The external surface area of the filler can be estimated from a psd by summing the area of all of the equivalent spheres. This method does not take into account the morphology of the surface. It usually yields low results which provide Htde information on the actual area of the filler that induences physical and chemical processes in compounded systems. In practice, surface area is usually determined (5) from the measured quantity of nitrogen gas that adsorbs in a monolayer at the particle surface according to the BET theory. From this monolayer capacity value the specific surface area can be determined (6), which is an area per unit mass, usually expressed in m /g. 

Electrophoresis (qv), ie, the migration of small particles suspended in a polar Hquid in an electric field toward an electrode, is the best known effect. If a sample of the suspension is placed in a suitably designed ceU, with a d-c potential appHed across the ceU, and the particles are observed through a microscope, they can all be seen to move in one direction, toward one of the two electrodes. AH of the particles, regardless of their size, appear to move at the same velocity, as both the electrostatic force and resistance to particle motion depend on particle surface this velocity can be easily measured. 

Fig. 3. Adsorbed cationic polymer forming charge patch on particle surface (32).

M ass Transfer. Mass transfer in a fluidized bed can occur in several ways. Bed-to-surface mass transfer is important in plating appHcations. Transfer from the soHd surface to the gas phase is important in drying, sublimation, and desorption processes. Mass transfer can be the limiting step in a chemical reaction system. In most instances, gas from bubbles, gas voids, or the conveying gas reacts with a soHd reactant or catalyst. In catalytic systems, the surface area of a catalyst can be enormous. Eor Group A particles, surface areas of 5 to over 1000 m /g are possible. 

Ga.s-to-Pa.rticle Heat Transfer. Heat transfer between gas and particles is rapid because of the enormous particle surface area available. A Group A particle in a fluidized bed can be considered to have a uniform internal temperature. For Group B particles, particle temperature gradients occur in processes where rapid heat transfer occurs, such as in coal combustion. 

Fundamental models correctly predict that for Group A particles, the conductive heat transfer is much greater than the convective heat transfer. For Group B and D particles, the gas convective heat transfer predominates as the particle surface area decreases. Figure 11 demonstrates how heat transfer varies with pressure and velocity for the different types of particles (23). As superficial velocity increases, there is a sudden jump in the heat-transfer coefficient as gas velocity exceeds and the bed becomes fluidized. 

Aerosol-Based Direct Fluorination. A technology that works on Hter and half-Hter quantities has been introduced (40—42). This new aerosol technique, which functions on principles similar to LaMar direct fluorination (Fig. 5), uses fine aerosol particle surfaces rather than copper filings to maintain a high surface area for direct fluorination. The aerosol direct fluorination technique has been shown to be effective for the synthesis of bicycHc perfluorocarbon such as perfluoroadamantane, perfluoroketones, perfluoroethers, and highly branched perfluorocarbons. 

Surfa.ce, Any reaction between two powder particles starts on the surface. The amount of surface area compared to the volume of the particle is, therefore, an important factor in powder technology. The particle—surface configuration, whether it is smooth or contains sharp angles, is another. The particle surface area depends strongly on the method of production, as shown in Table 1. The method of production usually determines the particle shape. 

Although the size separation/classification methods are adequate in some cases to produce a final saleable mineral product, in a vast majority of cases these produce Httle separation of valuable minerals from gangue. Minerals can be separated from one another based on both physical and chemical properties (Fig. 8). Physical properties utilized in concentration include specific gravity, magnetic susceptibility, electrical conductivity, color, surface reflectance, and radioactivity level. Among the chemical properties, those of particle surfaces have been exploited in physico-chemical concentration methods such as flotation and flocculation. The main objective of concentration is to separate the valuable minerals into a small, concentrated mass which can be treated further to produce final mineral products. In some cases, these methods also produce a saleable product, especially in the case of industrial minerals. 

In acidic media, ie, pH = 3, 2 piotonates to give HO 2 (pK 4.88 (48)). Other reactions that occur on the Ti02 particle surface and which are... 

The extent of the changes in the electronic characteristics and in the very nature of the Ti02 particle surface dictates the events that take place along the photo oxidative path to mineralisation of organic substates. 

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